Mixed hydroxy fatty acid-unsaturated fatty acid thickened grease compositions



L. F. KXNG 2,820,762 MIXED HYDROXY FATTY ACID-UNSATURATED FATTY ACID THICKENED GREASE COMPOSITIONS Original Filed April 1, 1952 .isczcwam La I 1 4L125 SKA/amber Q55 (ii/ Mttorrug MDED HYDROXY FATTY AClD-UNSATURATED FATTY ACID THICKENED GREASE COMPOSI- TIONS Laurence F. King, Sarnia, Ontario, Canada, assignor to Esso Research and Engineering Company, a corporation of Delaware Continuation of application Serial No. 279,831, April 1, 1952. This application June 14, 1954, Serial No. 436,354

18 Claims. (Cl. 252-18) The present invention relates toanti-friction bearing lubricating greases and particularly to heavy duty lubricating greases which are particularly suitable for the long life lubrication of railway car journals mounted in roller bearings, and for comparable heavy machinery. Roller bearings are coming into increased use in railway rolling stock, because they reduced starting power requirements considerably. They have been found rather diflicult to lubricate satisfactorily for periods of long service. Such lubrication is highly essential for railroad service.

in the prior art the plain bearing journals of railroad cars have usually been lubricated with oil applied to fibrous material such'as cotton waste and the like. These relatively new types of bearing, of course, cannot be lubricated with oil and waste in the conventionalway. Since lubricating oils drain away from roller bearings and leave them unprotected it is necessary to use thickened oils or greases. Among other requirements, greasesfor railroad roller bearing application must be highly resistant to oxidation. Ordinarily they are required to pass a drastic performance test in this respect. Some railroads require that greases must give satisfactory lubrication for 350,000 miles which amounts to three to four years of average normal operation. It is important that such lubricants show no substantial tendency to thicken during this period r to harden in consistency. This hardening factor appears to be particularly critical in certain of the Hyatt types of roller bearing which are commonly used for railroad car journals. To a lesser degree, however, the same requirements apply to other standard antifriction bearings of popular manufacture which are widely used.

Some of the bearings mentioned above are designed so as to require a soft grease which can be pumped at the temperature of operation through an orifice to a friction thrust block. The temperature of operation, of course, varies under different conditions but usually does not exceed about 175 F. Standing equipment, of course, may drop to temperatures much below zero in some cases.

Many conventional greases which perform entirely satisfactorily in normal ball or roller bearing service are quite unsuitable for lubricating some of the bearings mentioned above as used in railroad car journals. The lubricants fail commonly because the severe shear or mechanical working which occurs in the bearings hardens the greases to an intolerable degree. Generally speaking, a hardness indicated by ASTM penetration below 200 exceeds the allowable limit. In other instances a grease which hardens sufiiciently in other bearings will be worked out or thrown out of the hearings to some extent, and to this extent will be replaced with a softer portion of the grease. This does not occur in some of the Hyatt type bearings. When hardening occurs in these cases, the greast does not reach the thrust block at all. Bearing failure frequently ensues in such circumstances. This has been demonstrated in actual railroad tests on one of the larger railroads in recent years.

A further factor which makes many lubricating greases nited States atent' ice unsatisfactory is the exposure to water which so often occurs in railwayservice. Satisfactory greasesmust show a reasonably good resistance to the washing action of water. Although-bearings, especially those used in railroad service, are designed to keep out water to a good degree, water often penetrates the bearinghousings under unusual conditions. Greases must be reasonably stable in consistency in the presence of. water. The soap. con-- tent. must not be: washed out or the grease emulsified to an unduedegree- Since railway rolling stock is'used invariousseasons. and under various operating conditions the grease must provide adequate lubrication over a wide temperature range. This places further limitations. upon the type of.- grease that canbe used.

Experience has shown that greases having the follow ing general characteristics are satisfactory for the roller bearings of railroad car journals. In general, they have been approved by the railroads:

(a) They should contain a soda or soda-lime soap of a fat or fatty acid preferably having an iodine number less than 30, preferably between 15 and 30. This is' to impart reasonable water resistance to the grease; those from high iodine number fat have a greater tendency to emulsify in the presence of water.

(-17) The soap content should be low (approximately 7 to 17%, 8 to 13% being preferred) to give an ASTM worked penetration of 340-370 and thus ensure good pumpability throughout the temperature range encountered.

(c) The mineral oil shouldbe of fairly highviscosity index, at least 50 and preferably or higher, so asto obtain optimum performance over a wide temperature range and to impart better oxidation characteristics. The desired viscosity range of the oil is- 300-1000 S. S. at F., preferably 300 to500, though a slightly higher viscosity of oil can be used in the warmer climates.

(d) Other requirements such as oil separation characteristics, corrosion promoting tendencies, and mechanical stability are. also important and are discussed below.

It has recently been demonstrated that a very great improvement. in the. oxidation characteristics of lubricating. greases in high temperature service can be attained by adding sodium phosphate. This applies particularly to the soda soap greases and soda-limesoap greases which are about equivalent in this respect. In a copending application, Serial. No. 230,415, filed June 7, 1951, now abandoned, by the present applicant and a co-inventor, a. number of examples are given showing the improvement in oxidation resistance obtained by using sodium phosphate. Sodium phosphate also improves the yield or the consistency for a given soap content and it makes it possible to formulate a stable grease, using as a base oil a highly refined mineral lubricating oil of high viscosity index.

In the prior art thelow viscosity index oils have usually been chosen for the manufacture of'lubricating greases. They are less susceptible to oil separation and they'form a more stable grease structure than the oils of high vis'-- cosity index. For lubricating service over a wide range of temperatures, however, the oils of high viscosity index] have obvious advantages. Oneaspect of the presentinvention is the discovery of a method by which oils of'higl'r viscosity index may be used to make high quality lubricating greases for antifriction bearings which can withstand severeservice over long periods of time.

on working. In particular, it is found to. be advantageous to use IZ-hydroxy stearic acid-as a soap forming constituent.

In orderto stabilize the soap in an oil of high viscosity index an attempt was made, to use a small vproportion of sodium sulfonate asthe'dispersing'agent.- A grease employing the soda-lime soap of 12-hydroxy stearicacid and a'mineral lubricating oil of high' viscosity index was prepared using 0.8% by weight, o'n-a dry basis, of sodium sulfonate This productappeared -to be suitable in all respects-exceptthat excessive hardening took place when atrace of water was present in the grease and the product was heated to 200 F. for '1 hour and cooled without agitation. Quantities of water of the order of 0.1% were sufficient' to cause this objectionable hardening. The product became my and crumbly, approaching ablock grease in hardness (33 micro penetration approximately 150 rnmE/ 1'0 ASTM penetration) and-was entirely unsatisfactory for lubricating journal roller bearings of the type described abovep The product described above was worked in a standard ASTM grease worker and restored approximately to its original consistency but it would'not be usable in a standard l-lyatt roller bearing of railroad journaltype and was considered unsatisfactory for service.

i -It appears that greases'for bearing service of the type under consideration preferably should be relatively soft, having a worked penetration not'greater than 340 to 370 mm./l0.' Further experimental work was required. to overcome the hardening phenomenon;v It was found that the hardening phenomenon was'more or less peculiar to a composition containing 12 -hydroxy" stearic acid soap of lime and soda (orof soda base alone) with sodium phosphate in the presence of a trace of water. The mixed soda-lime grease has somewha't'superior water resistance over straight soda base grease. V

When no water was present-several-greases were found to be quite free from hardening in service. Thus, the con ventional soda and soda-lime greases prepared from stearic or oleicl acids or fats containing them were satisfactory. This wastrue also of greases'prepared from 1 2-hydroxy stearic acid butcontainingno sodium'phosphate, as well Attempts were made to improve the grease by substituting other fatty materials for part of the 12-hydroxy stearic acid. When 25% of the acid was replaced with stearic acid there was little improvement. Replacement of a major part of the 12-hydroxy. stearic acid with'stearic gave some improvement in .hardening tendency but re-.

v sulted in considerable loss in mechanical stability to shear. Furthermore, it increased bleeding tendencies on storage.

Stearic acid, alone or in combination with sodium sulfonate, was also found to be unsatisfactory since it gave a grease of poor yield, 16.6% soap requ red for a worked penetration of 355 mm./ 10, and poor storage stability,

the grease softening on storage. 7 p q According to the present invention it has been discovered that a replacement of a minor part, approximately 15 to 35%, of the 12-hydroxy stearic acid with an'unsaturated fat or fatty acid'will practically eliminate. the hardening tendency and at the same time improve-me, chanical stability. The yield is lowered somewhat by the incorporation of unsaturated fatty acidaalone. This can be restored, however, in a grease of approximately 12 to 13% soap content, by addition of a'small quantity, about 7 0.5 to 0.7% by weight, based on the'total composition,

of a hydroxy compound, preferably glycerine or ethylene 'lycol. 1 e. those of molecular weight below about 1500 or so.

The maximum amount of 12-hydroxy stearic acid that i can be replaced with unsaturated fat or fatty acid is limited.

. to 30 iodine number.

In general, it must be a minor proportion as noted above and the mixture should have an iodine number between.

about -15 and 40 before saponificatiompreferably a 15 It appears to be necessary to have present a small amount of the glycerine or similar hydroxy V unsuitable.

' trations as high as 15%.

as conventional greases-containing sodium phosphate, and

conventional greases containing sodium phosphate plus sodium sulfonate. q, f I a However, the cornbination of greases'prepared from l2'-hyd roxy stearic" acid with sodium phosphate were unrepresented 'infthese photographs was the soda-lime base product, the soap being derived from 12-h ydroxy stearic ac1d,-containing about 1% sodium phosphate. Fig. 1

' shows the grease (K-2387 before oil'dilution) before the hardening test'and Fig. 2 shows the same grease after the hardening test; 7 Long soap crystals which existed in the original gr'easewere disrupted and broken down into much shorter. ones by the test procedure. The very small quantity, of water, much less than stoichiometrical proportions, indicates that hardening is not duesimply tohydration of the soap. Manychanges-in the formulation were made in attempts to overcome this difiiculty. Wh e'n the sodiumsulfonate was omitted a product of low yield was obtained.-

It had a 375 mm. /10 penetrationwith 16%, soap content.

. It was too soft when new and became excessively hard in roller bearing service. Furthermore, the soap was not well dispersed. :Plasticizing agents such as glycerine, diethylene' glycol, polyethylene glycol, diethanol amine, methyl cellusolve,and the like were totally ing t t ivfi in limiting the hardening tendency. i

compoundin order to obtain good consistency at relatively low 'soapcontents. Mixturesof conventional saturated fatty acids such as stearic acid and oleic acid are entirely Such greases are still fluid with soap concerts Furthermore, they have little resistance to mechanical breakdown on working. a

The combination of soap of 12'-hydroxy stearic acid witha minor proportion of unsaturated fat or fatty acid of the C 2 to C range, such as oleic acid'or acidless tale low, cottonseed oil and'like materials is preferred; The composition should include 0.5 to 4% by weight of trisodium phosphate'and 0.2 to not more than 1% of glycerine or glycol. For service under varying temperature conditions, mineral lubricating oils of high viscosity index, of at least 80 and preferably a little higher should be used asthe liquid constituent. Oils having a viscosity index between 50 and 751are easier to thicken to stable gels and are quite satisfactory for most service. Greases; ras f01- of higher viscosity index may be manufactured lows, according to the present invention.-- 1

The fatty acids and an approximately equal weight'of mineral oil are chargedto a grease kettle. This portion of the oil may be of preferably slightlyflower viscosity 1 index than the'average of-the final'productto facilitate formation of asoap concentrate. Thus; oil of about .50

to viscosity index orfslightlylower may be used at first. The mixture is heated'to about 150 F. and; the saponifying ,agentor agents areadded, together with water. Thus, for a soda-lime grease'appropriate proportions of NaOH and lime are added in aqueous solution or slurry. The resulting soap is cooked to a temperature of 300 to 325 F. (using about pounds steam pressure in a steam cooker) until the product isthoroughly dry. At this point the free alkali contentof'the soap should be approximately 0.110 03 It is'p'refer'red'that the product not be acidic at this point because this results in poor color stability and loss of yield." f

The sodium phosphate (which is preferably 'trisodium phosphate, though disodium phosphate may be used. in cases where oxidation life is less important) is then added in aqueous solution. The soap-saltmixture is cooked until "(5 a complex is f-formed which is essentiallyanhydrous.

The lower polyethylene glycols also can be used, I

Small quantities of water may be added at the cooking temperature, however, to insure optimum dispersion of the salt in the soap and of the complex in-the oil. The product should be heated further until thoroughly dry.

Thereafter the remainder of the lubricating oil is added slowly. A further proportion of the lower viscosity index oil may be used first, followed by addition of oil of higher viscosity index to raise the average viscosity in- TABLE I Efiect of heating on the micro penetration of soda-lime greases containing sodium phosphate 1 Micro penetration (taken at 77 F.)

Soap Grease Grease+0.25% Desig- Soap stock wt. Plasticizing agent, A. S. T. M., water nation percent wt. percent wkd. pen.

Orlgi- After 1 Orlgi- After 1 mil hr. at nal hr. at

K2387 IZ-Hydroxy stearic acid 10. 5 Sodium sulphonate 345 152 r09 13s as K2388 Stearic acid 16.6 Sogjifmgi SgbhODB-W 355 165 132 172 92 y K-2390- Staaric acid (3 parts), 12-0H stearic acid 15. 0 S0 dium sulphonate 337 137 103 117 74 or K-2429. 120% stearic acid (3 parts), stearic acid 10. 6 Glycerin, 0.5 345 88 87 44 1 ar I K2426- 128% stgearic acid (3 parts), oleic acid 19.2 340 145 122 106 par 14-2427" 128B: searic acid (3 parts), olelc acid 12.6 Glycerin, 0.6 355 3 152 102 137 110 par 1 Prepared in laboratory at 300325 F. using 400 S. S. U. viscosity at 100 F., 85 V. I. mineral oil. All by weight Na3PO4 (anhydrous) as a complex with the soap. Ratio of soda to lime soap is constant (4:1).

2 Original grease contains 0.1% water.

greases contain approx. 1%

No'rn.A grease approved for railroad car journal service changed in micro penetration on this test from 160 to 82; in presence of 0.25% E20, item to 190.

dex of the final product. The product is then cooled with stirring and at a temperature of approximately 275 F.. the glycerine or glycol is added, followed by addition of a very small amount of water (about 0.1% preferably) Table II shows the specifications of various users and the results obtained with various commercial products 40 in comparison with the product just described which is designated New Product. Blanks indicate that the data were not obtained TABLE II F ormzzlae and inspections of grease for railroad car journai box roller bearings Railroad specification 1 'Iimken spec'n Approved product New product Formula, percent by wt.:

12-hydroxy stearic acld. 9.7. Oleic acid 2.9. Sodium hydroxide (dry) 1.8. Hydrated lime 0.4. Trisodinm phosphate 2.6.

Mineral oil (300 S. U. S., 40.0.

Soda or soda-lime soap-refined General Soda-lime soap refined oil Soda-lime soap refined oil oil-i-oxidation inhibitor; no oxidation inhibitor, no oxidation inhibitor, no fillers. fillers. fillers.

Mineral 011: 1

' Flash, F 340 (min) Fire, F 380 (min) V/100 F., S S U- 450-800 (desired) V/ 0 F., 5075 V. 80 (min.)

Pour,F 0(max) s a {Min ratio sodalime of 6:1

o p Mex. content 13% Approx. 10%

Oxidation inhibitor Road service tests of 350,000

Free alkali, percent I Colour 3 Formulae and inspectians of grease for railroad car journa l box roller bearings 7 seam Railroad specification l Tiinken specv'n Approved product 7 New'prodnct Oil separation (bleedingk (man) (no bleeding)--.

Pass road service test when mixed with approvedgreasesv mesh galvanized screen-for 2/4 hours at 210 F. Bleed-. ing, percent.

, (b)'185 g..grease in 28 mesh galvanized cone for 100 hours I Railroad specification is based on the requirements of a large eastern railroad in the United States and Canada.

TABLE III Grease hardening tests on car Journal greases 1 Time re- 1 quired to Designation Soap stock reach mlcropenetration of 50 on grease, hours '12-hydroxystearicacid 1,500

Stearic acid 450 Stearic acid .(37 parts) 1,200 7 12-011 stearic acid (1 l part). 12-0H stearic acid (3 1, 750

parts) stearic acid (1 l part). K-2427 12-0H stearic acid (3 3,000+

parts) oleic acid (1 part). Approved product (railroad 1, 400

specification). t

1 N. L. G; I. spindle test bearing packed with grease and placed in oven at200F, r m h r The results inTable III are, of course, obtained from accelerated tests at temperatures of 200 F. which are substantially higher and hence much more severe than in actual service.

It will be understood that the lubricating oil may include conventional anti-oxidants, metal deactivators,

tackiness agents, viscosity index improvers, and other.

usual additives in conventional-quantities.

This applicationisa continuation of copending appli- 35% by weight of oleic, acid, said soap also containing about 0.5-4% by weightbased on totalsoap of a sodium phosphate having at least 2 sodium atoms per molecule, and 0.2 to 0.9% of a hydroxy compoundselected from the class which consists of glycerine and glycol.

5. Composition according :to claim 4wherein said phosphate is trisodium phosphate. V

6. A heavy duty long life lubricant-composition of soft grease consistency for railway journal bearings and the like, consisting essentially of about 80 to 92% by weight, based on the total composition, of mineralbase lubricating oil of'200 to 600 S S; U. viscosity at 210 F. and average viscosity index at least 80, 7 to 17% of soda-lime soap composed of about 65-85% by weight of ber between 15 and 40, 0.5 to 4%,.base'd on total soap; of trisodium phosphate complexed withsaid-soapfand.

0.2 to not more than 1% total of glycerine plus ajtrace' ofwater.

7. Composition according to claim 6 containing aboutv 10 to 14% soap and 2 to 3% trisodium phosphate'on a hydrate salt basis.

8. Process for manufacturing a lubricating "grease "which comprises making a concentrate of'a grease-mak- H ing sodium soap, in mineral lubricating oil of viscosity index belowthatdesired in the final product, adding a 1. A heavy duty lubricating grease composition consisting essentially oi about 80-92% by weight'cf ja eral base lubricating oil of viscosity index of at least 50, 7 to 17% by weight, based o'n'the total com'po'sitionof a sodium containing-soap derived from a fatty-material with iodine number between" 15 and' lO, said fatty'material comprising about -85% by weight of IZ-hydroxy stearic acid and about 15-35% by weight of unsaturated fatty acid of the C to C range, and 0.2 to 1.0% of a hydroxy compound selected from the classwhich con-.1.

sists of glycerine and glycol,

2. Composition according to claim 1 containing 0.5 to

4%, based on theweight of'thc' soap, of a sodium phossaid fatty material comprising about65-85%' by weight phate containing at least two atoms of sodiumzper molecule;

3. Composition according to claim 2 wherein said sodium phosphate is trisodium phosphate, V

4. A lubricau'nggrease composition consisting essen- 85% by'weight of IZ-hydroxy stearic acid and about 15- gly'cerine and glycols.

11. Composition according to *r'ninor oxidation-inhibiting proportiorilof a sodium phos- -phate containing at least two atoms-of sodiunr'per sodium phosphate of; at c leastptwo, sodium atoms -per.

molecule, cooking to dehydrate, workingadditional; oil of higher viscosity. index to bring the-averag vis t cosity index up to at le a st and to adjust the pap content of the final product to be in tberan'gc-ofl'l f wt, percent, cooling while working and adding 0:2't 0.9% by weight, based on the total composition, of-ajhy'clroxy material selected from the class which consists of glycrineQ ethylene glycol and polyethylene glycol during-cooking c 9. The process of claim 8 in'whichsaid soap is-amiXr, ture of sodium-containing.soaps of 12-hydroxy 'stearic acid and an unsaturatedfatty acid of the C -C range..

10. A heavy duty lubricating grease composition com-. prisinga major proportion joflalmineralib ase lubricating oil of viscosity'indexof at least-50, in the rangelof 7 to 17 wt. percent of a sodium-containing soap derived irorn a fatty material withiiodine'number between 15 and ,40,

'of a hydroxy fatty acid and about 15-35%;by weight of unsaturated fatty acid of the C to ,C 'range, and a i still lesser grease-yield improving proportion of ,ahydroxy sists of compound selected from the class whichco claim "10 containing a molecule.

12. Composition according to claim 11 wherein said sodium phosphate is trisodium phosphate.

13. A lubricating grease composition comprising a major proportion of a mineral base lubricating oil having a high viscosity index of at least 80, and in the range of ,7 to 17 wt. percent of a soda-lime soap composed of about 6585% by weight of a hydroxy fatty acid and about 15-35% by weight of oleic acid, said soap also containing a minor oxidation-inhibiting proportion of a sodium phosphate having at least 2 sodium atoms per molecule, and a minor grease-yield improving proportion of a hydroxy compound selected from the class which consists of glycerine and glycols.

14. Composition according to claim 13 wherein said phosphate is trisodium phosphate.

15. A heavy duty long life lubricant composition of soft grease consistency for railway journal bearings and the like, comprising a major proportion of mineral base lubricating oil of 200 to 600 S. S. U. viscosity at 210 F.

and average viscosity index at least 80, in the range of 7 to 17 wt. percent of soda-lime soap composed of about 6585% by weight of a hydroxy stearic acid and about 15-35% by weight of oleic acid, said mixture of acids having an iodine number between 15 and 40, a minor oxidation-inhibiting proportion of trisodium phosphate complexed with said soap, and about 0.2 to about 1% total of glycerine plus a trace of water.

16. Composition according to claim 15 containing about 10 to 14% soap and 2 to 3% trisodium phosphate on a hydrate salt basis.

17. Process for manufacturing a lubricating grease which comprises making a concentrate of a grease-making sodium soap in mineral lubricating oil of viscosity index below that desired in the final product, adding a sodium phosphate of at least two sodium atoms per molecule, cooking to dehydrate, working in additional oil of higher viscosity index to bring the average viscosity index up to at least 50 and to adjust the soap content of the final product to be in the range of 7 to 17 wt. percent, cooling while working and adding a minor grease yield-improving proportion of a hydroxy material selected from the class which consists of glycerine, ethylene glycol and polyethylene glycol during cooking.

18. The process of claim 17 in which said soap is a mixture of sodium-containing soaps of a hydroxy stearic acid and an unsaturated fatty acid of the 0 -6 range.

References Cited in the file of this patent UNITED STATES PATENTS 2,450,149 McCarthy Sept. 28, 1948 2,455,659 Duncan et a1. Dec. 7, 1948 2,468,099 Morway Apr. 26, 1949 2,581,127 Morway et al. Jan. 1, 1952 2,678,918 Bondi May 18, 1954 

4. A LUBRICATING GREASE COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 80-92% BY WEIGHT OF A MINERAL BASE LUBRICATING OIL HAVING A HIGH VISCOSITY INDEX OF AT LEAST 80, AND ABOUT 8 TO 13% BY WEIGHT, BASED ON THE TOTAL COMPOSITIN, OF A SODA-LIME SOAP COMPOSED OF ABOUT 6585% BY WEIGHT OF 12-HYDROXY STEARIC ACID AND ABOUT 1535% BY WEIGHT OF OLEIC ACID, SAID SOAP ALSO CONTAINING ABOUT 0.5-4% BY WEIGHT BASED ON TOTAL SOAP OF SODIUM PHOSPHATE HAVING AT LEAST 2 SODIUM ATOMS PER MOLECULE, AND 0.2 TO 0.9% OF A HYDROXY COMPOUND COMPOUND SELECTED FROM THE CLASS WHICH CONSISTS OF GLYCERINE AND GLYCOL. 